C O M M U N I C A T I O N S
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a
p-MeO)dppp was employed. b The reaction was run at 90 °C. c Isolated
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(
as its methyl ester.
2
employed instead of [Rh(OH)(cod)] (eq 3). Importantly, further
,4-addition of alkenylboronic esters to the produced R,â-unsatur-
ated carboxylic acid derivatives was not observed in these reactions.
As alkenylboronic esters can readily be synthesized via hydrobo-
ration of the corresponding alkynes with catecholborane, followed
by a trans-esterification or coupling reaction with the corresponding
alkenyl halides or triflates with tetra(alkoxo)diborons, substrates
containing various functional groups would be applicable to this
carboxylation reaction.
(
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1
6
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In summary, we have succeeded in developing a rhodium-
catalyzed carboxylation reaction of aryl- and alkenylboronic esters
under mild conditions. As organoboronic esters are easily available
without using organolithiums or Grignard reagents, various func-
tional groups are tolerated in this reaction.
(10) de la Herr a´ n, G.; Mba, M.; Murcia, M. C.; Plumet, J.; Cs a´ k y¨ , A. G. Org.
Lett. 2005, 7, 1669.
(
11) It is not yet clear whether the product in the reaction mixture is Cs
carboxylate or boron carboxylate (or its fluoroborate salt). We are currently
under study to clarify the exact mechanism of the reaction.
(
12) After the catalyst, dppp, CsF, and the substrate were mixed in dioxane
Acknowledgment. This research was partly supported by a
Grant-in-Aid for Scientific Research from the Ministry of Education,
Culture, Sports, Science, and Technology of Japan.
under 1 atm of CO
2
using a balloon, the reaction mixture was cut off
from the balloon, kept closed, and heated at 60 °C. Although the
temperature is below the boiling point, sufficient care should be taken
for high pressure. The reaction was carried out behind a safety shield.
Supporting Information Available: Preparative methods and
spectral and analytical data of compounds 1-4. This material is
available free of charge via the Internet at http://pubs.acs.org.
(13) Most reactions could be carried out under 1 atm of CO
without problem.
2
using a balloon
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VOL. 128, NO. 27, 2006 8707